Organic sulphonates and method of making



- Patented Apr.'17, 1945 ORGANIC S ULPHONATES AND METHOD OF MAKINGLeland James Beckham, Geddes, N. Y asslgnor to The Solvay ProcessCompany, New York, N. Y., a corporation of New York No Drawing.Application December 30, 1941,

\ Serial No. 424,941

16 Claims.

This invention relates to organic sulphonates of general utility and ofparticular value for use as detergents, wetting agents, dispersingagents, emulsifying agents and the like, and to methods for themanufacture of such products.

In my. application Serial No. 221,707, filed July 28, 1938, issued as U.S. Patent 2,265,993 on December 16, 1941, -I have described themanufacture of organic sulphonate products by forming an additionproduct of a nitrosyl halide with an unsaturated aliphatic compound orwith mixtures thereof and reacting the addition product with alkalisulphite so as to replace the halogen atom with a sulphonate radical.Such products will be referred to hereinafter as nitrosationsulphitationproducts."

My application Serial No. 424,940 of even date, entitled Derivatives ofunsaturated compounds and methods of making issued as United StatesPatent 2,336,387 on December 7, 1943, relates to the manufacture ofnitrosation-sulphitation oleflns at the lower end of this rangeexcelling products from carboxylic-substituted unsaturated hydrocarbonsand mixtures thereof.

The present invention is concerned with such products and particularlywith an improved I process whereby products having superior qualitiesmay be obtained. The products of the present invention comprise organicsulphonates containing in addition to the sulphonate radical asulphamate radical. I have found'that the-presence'of the sulphamateradical in such products contributes materially to the utility of theseproducts as detergents, wetting agents, emulsifying agents,'and thelike.

In the manufacture of organic sulphonates by the. specific proceduresdescribed in my application Serial No. 221,707 there is some formation-fortl'r-in my applications Serial N0. 221,707 and Serial No. 424,940,referred to above. Nitrosyl chloride addition products of organiccompounds containing non-aromatic C=C linkages, particularly olefins andtheir carboxylic derivatives such Of thev olefins, the mono-olfinscontaining between 16 and 23 carbon atoms are especially suitable forthe manufacture of cleansing agents, the

in wetting and foaming power, those near the middle excelling as. lowtemperaturewashing agents, and those at the higher end excelling aswashing agents for relatively high temperature washing. However, thereare no rigidly fixed boundaries between the materials suitable forwetting agents and those suitable for detergents, and the molecularstructure may influence the properties of the products one way oranother to shift the boundary between those materials most effective asdetergents and those most effectlve as wetting agents. Moreover, thepresence of materialsmost suitable as wetting and foaming agents in aproduct intended primarily for cleansing may have substantial advantagesring fats, and'oils, such as tallow, palm oil, cocoa-- in acceleratingwetting, and holding soil, thus expediting cleansing operations.

The oleflnic compounds may bestraight chain compounds or secondary ortertiary branched chain compounds, and may contain one or more doublebonds per molecule. The double bonds may be located in a terminalposition or in an intermediate position. Compounds most valuable fordetergent purposes maybeob'tained from olefins' andcarboxylic-substituted olefins containing an olefinic linkage at the endof a carbon chain of at least 8 carbon atoms.

The source of the olefinic compound may be animal, vegetable, 'ormineral. Thus suitable olefins may-be prepared by dehydrating alcoholsobtained by hydrogenation of naturally occurnut oil, olive oil, or thecorresponding free acids, or the oleilns-may be'prepared by the Fischer-Tropsch synthesis or by cracking waxes or by cracking ordehydro-genating natural or synthetic (Fischer-Tr'opsch) petroleum orpetroleum fractions or by halogenating and dehydrohalogenating suchmaterials or by polymerizing low molecularweight olefins.

Olefinic mixtures containing olefins and sat- ,vention.

urated hydrocarbons derived 'from natural or synthetic (Fischer-Tropsch)petroleum immediately or by thermolytic treatments constitute highlysatisfactory initial materials for the manufacture of the products ofthe present in- Thermolytic treatments which have been foundto yieldlarge proportions of the desired olefins are catalytic and non-catalyticbinations thereof. The preferred oleflnic mixtures, comprising for themost part hydrocarcracking, catalytic dehydrogenation, and combonscontaining between wand 30 carbon atoms per molecule, may be Segregatedfrom less desirable products of the treatment by fractionaldistillation. Non-olefinic hydrocarbons may be permitted to remain andmay be separated after the sulphitation treatment as water-insolubleoils. The petroleum may be fractionally distilled prior to thethermolytic treatment to provide an oil containing an increasedproportion of the hydrocarbons containing 10 and more carbon atoms permolecule.

Examples of suitable olefins are cetene de-.

rived from spermaceti (and comprisingfor the most part cetene-l),2-methyl pentadecene-2, dodecene-l, pentadecene-7, tricosene-ll, non- Idecene-9, IO-methyl nondecene-9, and olefincontaining mixtures obtainedby cracking topped, crude, natural or synthetic petroleum or bydehydrogenating a petroleum distillate such as gas oil or by reactingcarbon monoxide and hydrogen in the presence 'of a catalyst such ascobalt (the Fischer-Tropsch synthesis). Some synthetic N-methyl .oleicacid amide, N-dimethyl oleic acid amideyoleic acid anhydride, oleic acidchloride,

oleic acid nitrile, N-allyl lauric acid amide, N- oleyl butyric acidamide, N-methyl N-oleylpropionic acid amide, N-ethyl N-oleyl acetic acidamide, N-methyl N-lauryl 4-hexenoic acid amide, N-decyl 3-pentenolicacid amide, 3-methyl-4-dimethyl-cyclopentane-l-carboxylic acid ester ofallylalcohol, A -3-methyl-4-dimethyl-cyclopentene-l-carboxylic acidester of butanol-l. Examples of other types of suitable unsaturatedcompounds are oleone and n-lauryl cyclohexene.

The NOCl addition products are believed to comprise largely organicnitroso chloro compounds having the chlorine atom andnitroso group uponadjacent carbon atoms (that is, attached to carbon atoms which formedthe nonaromatic C=C linkage in the parent unsaturated organic compound),their isomeric oximes, and probably the chloroderivatives formed bysubstitution of chlorine for a remaining hydrogen of the,nitroso-substituted carbon of, the nitroso chloro compounds, and dimersof the nitroso chloro compounds. A considerable proportion of theseproducts reacts further under the conditions of nitrosation to losenitrogen and form products such as alpha-chlorohydrins andalphachloro-ketones. Hence the nitrogen content of the addition productas .a whole may correspond to only 0.6 to 0.7 atom per ethylenic group.

In accordance with the preferred process of the present inventiomtheNOCl addition product of an organic compound containing at least onenon-aromatic k0 linkage is reacted with a mixture of alkali sulphite andbisulphite in a molecular ratio of normal sulphite to bisulphite between1:1 and 5:1 and in a proportion providing at least 2 /2, preferablybetween 2 and 5, sulphite radicals for each mol of addition product,whereby an organic sulphonate composition is produced comprisingsulphonated organic sulphamates in which the sulphonate and sulphamateradicals are attached to carbon atoms which formed the non-aromatic Cilinkage in the parent unsaturated organic compound. Three to foursulphite radical per mol ofv addition product are especially suitablesince they permit high efliciency without excessive dilution of theproduct by inorganic material. However the importance of the diluenteffect of larger proportions depends upon the use for which the materialis to be employed.

I have found that the presence of the alkali bisulphite within thelimiting ratios of normal sulphite to bisulphite specified has adirecting influence upon the course of the reaction and promotes theformation of products containing, in addition to sulphonate groups,monoor di-valent sulphamate radicals. Not only are the products producedby this process especially satisfactory 'as detergents, wetting agents,and the like but the valuable water-soluble products are produced inhigher yields than obtainable in the absence of the specifiedproportions of bisulphite. Moreover, they are produced with relativelylittle formation of colored by-products.

Examples of suitable alkali sulphites and bisulphites for use in thepreferred process for making the products of the invention are sodiumsulphite, sodium bisulphite, ammonium sulphite, ammonium bisulphite,potassium sulphite, and potassium bisulphite.

The sulphite-bisulphite solution may be prepared by employing thedesired proportions of the two ingredients separately prepared, or bytreat ing suitable materials to form the sulphite or bisulphite or bothin a reagent solution. Thus an aqueous sodium carbonate or sodiumsulphite solution may be treated with S0: or sodium metabisulphite toprovide a solution of sodium sulphite and sodium bisulphite inappropriate proportions. Or an aqueous sodium sulphite solution may beacidified with an acidic material, such as sulphuric acid, hydrochloricacid, a phosphorus acid, or an acid salt of such an acid, for examplesodium acid sulphate. The unreactive sodium salt formed may be retainedin the product as a filler, or as an adiuvant.

It is of advantage to employ a proportion of aqueous sulphite bisulphitereagent such that between 40 andlOO mols of water are present in themixture for each mol of nitrosyl chloride addition product. Also it isdesirable to employ from about one mol to about 15 mols of awater-soluble organic liquid, such as ethanol or isopropyl alcohol, foreach mol of addition product, as described in my application Serial No.424,942 of even date, entitled Manufacture of organic sulphonates.

The manufacture of the sulphonated sulphamates of the present inventionby reaction of nitrosyl chloride addition products with alkali sulphitebisulphite reagent may be conducted at temperatures between 60 C. and C.and at substantially atmospheric pressure, but higher or lowertemperatures or pressures may be employed.

Alternatively the sulphonated sulphamates of the present invention maybe prepared from suit-.

, able ketones by subjecting the selected ketone to monochlorlnation,reacting the monochlor ketone with sodium sulphite to form a sulphonatedketone, reacting the sulphonated ketone with hydroxylamineto form. thecorresponding sulphonated oxime, and either reacting the oxime withsulphur dioxide to form the sulphonated alkylidene sulphamate, orreacting the ,oxime with sodium bisulphite to form a, sulphonatedsulphamate bisulphite addition product, which by treatment with alkalimay be transformed into the sulphonated alkylidene sulphamate, orreducing th oxime to an amino alkyl sulphonate,and

sulphonating andv neutralizing toconvert the amino group to a sulphamategroup.

They also may be prepared from monosulphonated ketones by reactionthereof with sodium sulphamate to form directly thesulphonatedalkylldene sulphamates. a

A yet difierent method involves treatment of p an olefin, such as usedin the preferred process, with chlor-sulphonic acid to form thecorresponding chlor-substituted organic sulphonic acid, reacting theproduct with ammonia or sodamide to substitut an amino group for thechlorine, and sulphonating the resulting product. The al- Table 1 Yield,moi per cent 66 75 Relative color 6-7 4-5 Lime resistivity (pts. permillion) 700 850 Products A and B contain as their main organicconstituents sulphonated ketones. sulphonated amines, sulphonted'alkylidene sulphamates, sulphonated alkyl sulphamates, and bisulphiteaddition products of sulphonated alkylidene sulphamates. However inproduct B the sulphamate constituents constitute more than 50% of theorganic ingredients whereas product A contains between and less of thesulphamate kali-metal salt of the product may be obtained byneutralization. v

In those cases where the alkali-metal or ammonium salts are theimmediate products of sulphitation, the free acids may be produced byacidification and other metal salts or amine salts, such as alkalineearth metal salts, heavy metal salts, methylamine salts, ethanolaminesalts, and

pyridine salts may be formed by treatment with the appropriate base orby other known treatments appropriate to the formation of the desiredsalt from sulphonic and sulphamic acids.

Example 1 A nitrosyl chloride addition product freed from excess NOCl byaeration and prepared from a distillate fraction of cracked, toppedOlean crude which distillate (a Pennsylvania petroleum), fractiondistilled at pressures of 425 to 4 mm.

absolute at a constant temperature of 200 C.,- was divided intofractions. 'To one fraction ofthe nitrosyl chloride addition productthree mols of sodium sulphite, three mols of isopropyl alcohol, and '70mols of .water were added for each mol of addition product. Thetemperature of the mixture was raised to 85 C. over a-period' of onehour and maintained at this point for 23 hours. The oil phase was thendecanted ofi from the aqueous phase and the separated aqueous phase wasdiluted with between 2and 3 times its volume of water and was treated toremove remaining traces of residual oil by extraction.

An extractant such as petroleum naphtha or diethyl ether may be used.The resulting clear aqueous layer was then evaporated to secure thesolid sulphonated organic sulphamate product.

Another portion of the nitrosyl chloride addition product was mixed with3 mols of sodium sulphite, 1 mol of sodium acid sulphite, 3 mols ofisopropyl alcoholgifnd 70 mols of water per mol of addition product.This mixture was reacted in the same way as the first mixture and theaque A ous solution was separated from oil, purified, and

evaporated to obtain the solid sulphonated organic sulphamate product."The results of these two processes are tabulated below, designated A andB, respectively.

' 'tuting the nitrosyl chloride addition product of a dehydrogenated gasoil for the addition product employed in Example 2. The 1 followingtable shows the relation of the yield of detergent product to the ratiosof sulphite to bisulphite and total sulphite to olefin employed.

constituents based on total organic ingredients.

Example 2 Four portions of a nitrosyl chloride addition product of thetype employed in Example 1 were reacted with sodium sulphite with andwithout the addition of sodium bisulphite, otherconditions of reactionand recovery being the same.

The yield and color of the products are indicated I in the followingtable.-

I Table 2 Mols sul- Mols hisul- Yield 'lest phitv per phite per moi per213; e

incl olefin mol olefin cent 0 Example 3 The process of Example 2 wasrepeated substi- Two portions of a mixture of the nitrosyl chlorideaddition product derived from a dehydrogenated gas oil and .unreactedolefin were treated with sodium sulphite solution and with mixed sodiumsulphite bisulphite solution under otherwise similar conditions.

The yields for Tests Q and R in the following table are based on theolefin employed. Since a considerable amount of unreacted olefins waspresent, 'these yields are not directly comparable with other examplesbut are comparable with each other; The resultswere as follows:

Three portions of a nitrosylchloride addition product of adehydrogenated gas oil were treated in the same manner as in Example 4with the followin results Table 5 Mols sul- Mols bisul- Yield RelativeTest phite per phite per mol per color mol olefin 11) 110181111 cent 8.4. 0. 0 64 14-16 T 3. 0 l. 0 69 3-4 U- 2.5 1.5 68 3-4 The yields inTests S, T, and U are representative of the yields obtainable fromdehydrogenated gas oil olefin addition products. A comparison of theyields in Tests S and U with those in Tests Q and R indicates that themixture used in Example 4 probably contained between V5 and /1 of itsinitial olefin content unreacted.

Example 6 In order to follow the changes in composition of the reagentduring a process of the type de-' scribed in the preceding examples anitrosyl chloride addition product of a dehydrogenated gas oil wastreated with sodium sulphite and sodium sulphite bisulphite mixtures andthe sulphite and bisulphite concentrations were determined at intervalsby eletrometric titration of spot samples. The following results wereobtained.

Tablet Testv w x Y z Totalmolssulphite 3.00 3.00 3.00 3.00 4.00 MolsNazSOrat start... 3.00 2.67 2.33 2.00 3.00 M0lsNaHS08atstarL 0.00 0.330.01 1.00 1.00 Mol ratio 'Na SOz/NaHSO:

after- The following examples further illustrate the practice of thepresent invention. For simplicity of disclosure, the examples have beenset forth in tabular form. The general procedure 'for preparation of theproducts in each case was as follows:

A nitrosyl chloride addition product was prepared from each or thespecified carboxylic-substltutedoleflns by passing nitrosyl chlorideinto The reaction product, comprising the nitrosyl chloride additionproduct of the carboxylie-subwas heated gradually to the indicatedreaction temperature over a period of 1 hour. After completion of thesulphitation, two volumes water per volume sulphitation liquor wereadded and the resulting solution extracted 6 times with ethyl etherusing about. /2 part ether by volume per part original sulphitationliquor. Solid detergent was recovered from the extracted aqueous phaseby use of a laboratory double drum dryer.

Table 7 Mass values are expressed in gram atoms or mols per mol ofsubstituted olefin Examp18 7 Example 8 Example 9 Olcilnic material MolsN00] passed Nil-rosation time..." .i Nitrosation temp C (lram atoms Nintroduced. Gram atoms 01 introduced. M018 NagSO; Mols NaHSO;.

Oleic acid.

Ally] stenrate.

Sui hitation temp C. Mo per cent yield on olefinic material.

The products prepared by the nitrosationsulphitation procedure hereindescribed normally comprise, in addition to sulphonated alkyl andalkylidene sulphamates and bisulphite addition products of the latter,other sulphonated products such as sulphonated ketones and sulphonatedamines.

The feature of gradually raising the temperature of the reactants toreaction temperature during the sulphitation as described in connectionwith Examples 1, 7, 8, and 9 is the subject of my application Serial No.424,943 of even date, entitled Sulphltation of organic compounds.

It should be understood that in the appended claims where sulphiteradicals" are referred to it is intended to include both the sulphiteradicals of the alkali sulphite, i. e., the normal sulphite, and of thealkali bisulphite. It also should be understood that, where ranges aregiven, the ranges include the limits.

Iclaim:

1. As a new product, an organic sulphonate composition derived from anunsaturated organic compoundv containing a non-aromatic C=C linkage, andcomprising sulphonated organic sul-' phamates in which the sulphonateand sulphamat radicals are attached to carbon atoms which, in the parentunsaturated organic compound, formed said non-aromatic C=C linkage,

said composition containing at least one organic l radicals present inthe composition.

mate radicals are attached to carbon atoms which, in the parent.unsaturated organic compound, formed said non-aromatic C=C linkage; saidcomposition containing at least one organic sulphamate radical for eachtwo organic sulphonate 3. As anew product having surface-activeproperties,a mixture of organic sulphonates derivedyfrom an unsaturatedorganic compound containing a non-aromatic C=C linkage and between and30 carbon atoms per molecule, said mixture comprising sulphonatedorganic sulphamates in which the sulphonate and sulphamate radicalstween 10 and 30 carbon atoms per molecule, in-

cluding sulphonated alkylidene sulphamates, sulphonated alkylsulphamates, and sulphonated alkylidene sulphamate bisulphite additionproducts, said mixture comprising between one and two organic sulphamateradicals for each two organic sulphonate radicals present in th mixture.

7 5. As a new product having surface active properties, a mixture oforganic sulphonates comprising sulphonated organic sulphamates withbetween 10 and 30 carbon atoms per molecule, including sulphonatedalkylidene sulphamates, sulphonated alkyl sulphamates, and sulphonatedalkylidene sulphamate bisulphite addition products, saidmixturecontaining at least one organic sulphamate radical for each two organicsulphonate radicals present in the mixture.

6. As a new product having surface active properties, a mixture ofhydrocarbon sulphonate sulphamates, the hydrocarbon radicals of whichcorrespond to the mono-olefins present in an olefinic oil fractionconsisting essentially of hydrocarbons containing not less than 10 normore than 30 carbon atoms per molecule and obtained by thermolytictreatment of petroleum, said mixture containing at least one sulphamateradical for each two sulphonate radicals present in the mixture.

7. As a new product having surface active prop erties, a mixture ofhydrocarbon sulphonate sulorganic compound containing at least onenonaromatic C=C linkage with a mixture of alkali sulphite andbisulphite, the ratio of normal sulphite to bisulphite present in thereaction mixture during at least a portion of the reaction periodbeingbetweea 1 and 5 mols of normal sulphite for each mol of bisulphite.

10. In the manufacture of a sulphonated organic sulphamate product, theimprovement which comprises reacting a nitrosyl chloride additionproduct of an organic compound containing at least one non-aromatic C= Clinkage with an aqueous sulphite solution containing at least 2 /2sulphite radicals per mol of addition product present in the reactionmixture, the ratio of normal sulphite to bisulphite present in thereaction mixture vduring at least a portion of the reaction period beingbetween 1 and 5 mols of normal sulphite for each mol of bisulphite.

11. The method or making a sulphonated organic sulphamate product, whichcomprises reacting a .mtrosyl chloride addition product of an organiccompound containing at least one nonaromatic C=C linkage with an aqueousmixture of alkali sulphite and bisulphite the ratio of normal sulphiteto bisulphite present in the reaction mixture during at least a portionof the sulphitation being between 1 and 5 mols of normal sulphit foreach mol of bisulphite.

12.- The method of making a sulphonated organic sulphamate producthaving surface active properties, which comprises reacting the additionproduct of nitrosyl chloride and an organic compound containing at leastone non-aromatic C=C linkage and not less than 10 nor more than carbonatoms per non-aromatic C=C linkage with an aqueous mixture of alkalisulphite and bisulphamates, the hydrocarbon radicals of which correspondto the mono-olefins present in an olefinic 011 fraction consistingessentially of hydrocarbons containing not less than -16 nor more than28 nate sodium sulphamates, the hydrocarbon radicals of which correspondto the mono-olefins 7 present in an olefinic oil fraction consistingessentially of hydrocarbons containing not less than 16 nor more than 23carbon atoms per molecule" and obtained by thermolytic treatment ofpetroleum, said mixture containing between one and I two sodiumsulphamate radicals for each two sodium sulphonate radicals present inthe mixture.

9. The method of making a, sulphonated organic sulphamate product, whichcomprises reacting a nitrosyl chloride addition product of an phite theratio of normal sulphite to bisulphite present in the reaction mixtureduring at least a portion of the'sulphitation being between 1 and 5 molsof normal sulphite for each mol of bisulphite.

13. The method of making a sulphonated organic sulphamate detergentproduct, which comprises reacting the addition product of nitrosylchloride and an olefinic compound comprising not less than 10 nor morethan 30 carbon atoms per olefinic group with an aqueous mixture oralkali sulphite and bisulphite containing initially be tween -1 and 5mols of normal sulphite for each mol of bisulphite, in such proportionthat at least 2 /2 sulphite radicals are initiallypresent in the mixturefor each mol of nitrosyl chloride olefinic addition product.

14. The method of making a sulphonated organic sulphamate detergentproduct, which comprises reacting the addition product of nitrosylchloride and a mono-olefin comprising not less than 10 nor more than 30carbon atoms per molecule with an aqueous mixture of alkali sulphite.and bisulphite in such proportion that between 2 and 5 sulphite radicalsare initially present in the mixture for each mol of nitrosyl chlorideolefin addition product, and maintaining during a drocarbons containingnot less than 10 nor more cule and obtained by thermolytic treatment of10 petroleum, with an aqueous alcoholic alkali sulphite bisulphitesulphitation reagent containing between 1 and 5-mols of normal sulphitefor each mol of bisulphite, and between 2 and 5 sulphite radicals,between 1 mol and 15 mols of isopropyl alcohol and between 40 mols and100 mols of water for each mol of addition product present in themixture, and maintaining throughout substantially the entiresulphitation period a sulphite to bisulphite ratio within the aforesaidlimits.

LELAND JAMES BECKI-IAM.

